EP2994462B1 - Procede pour recuperer et ameliorer la production du meso-lactide a partir d'un flux contenant du lactide brut - Google Patents

Procede pour recuperer et ameliorer la production du meso-lactide a partir d'un flux contenant du lactide brut Download PDF

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EP2994462B1
EP2994462B1 EP14721873.9A EP14721873A EP2994462B1 EP 2994462 B1 EP2994462 B1 EP 2994462B1 EP 14721873 A EP14721873 A EP 14721873A EP 2994462 B1 EP2994462 B1 EP 2994462B1
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Prior art keywords
lactide
stream
meso
separation unit
distillation
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EP2994462A1 (fr
EP2994462B2 (fr
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Philippe Coszach
Denis Mignon
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Futerro SA
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Futerro SA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
    • C07D319/10—1,4-Dioxanes; Hydrogenated 1,4-dioxanes
    • C07D319/12—1,4-Dioxanes; Hydrogenated 1,4-dioxanes not condensed with other rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14—Fractional distillation or use of a fractionation or rectification column
    • B01D3/143—Fractional distillation or use of a fractionation or rectification column by two or more of a fractionation, separation or rectification step
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D9/004—Fractional crystallisation; Fractionating or rectifying columns
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D9/00—Crystallisation
    • B01D2009/0086—Processes or apparatus therefor

Definitions

  • lactide purification processes that usually comprise one or more integrated distillation, condensation and melt crystallization steps, like in US5,521,278 , US5,357,034 , US5,214,159 .
  • copolymers having a low content of D-enantiomers so broadening the range of grades of PLA which are needed to cover the different applications where PLA may be used ; those grades of PLA may contain various amounts of D-enantiomers ranging from about 1% by weight to more than 10% by weight, depending of the final use desired.
  • the crude lactide stream to be purified in accordance with the present process may comprise L-lactide, D-lactide, meso-lactide and mixtures thereof.
  • the crude lactide stream may contain mainly L-lactide.
  • the first step (a) of the recovery and production of mesolactide mainly under the form of a mixture meso-lactide and L-lactide, is carried out by passing the crude lactide stream (31) into a separation unit such as a distillation column (10).
  • a separation unit such as a distillation column (10).
  • the distillation column is a multi-stage distillation column.
  • the distillation column can be any type of known distillation column such as a tray column or a packed column.
  • the distillation column is a packed column.
  • the distillation column has a number of theoretical stages (NTS) in the range from 6 to 30.
  • the more volatile components of the lactide-containing stream (A) to be purified, forming stream (B), will be more easily evaporated through the top of the distillation column (10) than less volatile components such as L-lactide, oligomers of lactic acid and heavy impurities, which will be recovered through the bottom and the side draw of the distillation column.
  • the more volatile components generally identified as water, lactic acid, catalyst derivatives and gaseous lactide, like meso-lactide, will move to the upper part of the column and will be evacuated through pipe (1).
  • step (a) After evacuation of top stream (B) of column (10) through pipe (1) with the more volatile components, and the withdrawal of the less volatile components through bottom stream (C) through pipe (2), which is either hydrolyzed and sent back to the Lactic Acid Unit, or suitably recycled to the oligomerization step of the overall process, then, the important lactide-containing fraction of step (a) is suitably withdrawn from the distillation column (10) via a side draw, and constituting side stream (D) flowing through pipe (3) which is sent to a unit where the melt-crystallization (4) is carried out.
  • said lactide containing fraction withdrawn through the side draw by pipe (3) may contain in the range of from 90- 99,5 wt%, preferably in the range of from 95- 99 wt% of L- lactide and in the range of from 0-10 wt%, preferably in the range of from 0- 5 wt% meso-lactide, based on the total mass flow rate of the lactide containing fraction of the side draw.
  • the lactide containing fraction of the side draw has a ratio of L-lactide to meso-lactide in the range of from 1 to 100, preferably in the range of from 10 to 50.
  • a condensation unit may be implemented to treat the vapor phase lactide containing fraction.
  • melt crystallization (4) is carried out at a temperature which remains in the range of the crystallization freezing temperature and a temperature ranging well below the boiling point of lactide.
  • the meso lactide content in stream flowing in pipe (5) is in the range of from 0- 1 wt%, preferably in the range of from 0 - 0.5 wt%.
  • drain stream (F) which is mainly containing meso-lactide and L-lactide.
  • steps (b) and (c) of the process of the present invention top stream (B) flowing through pipe (1) coming from distillation column (10) is recovered and contains mainly meso-lactide, while drain stream (F) flowing in pipe (7) is also recovered and contains mainly L-lactide and meso-lactide.
  • both streams (B) and (F) are conveyed or combined and subjected to a distillation operation in one or more distillation operation system.
  • said system comprises a distillation column (20) which is a multi-stage distillation column.
  • the distillation column can be any type of known distillation column such as a tray column or a packed column.
  • the distillation column is a packed column.
  • said sole distillation column (20) is suitably operated at a temperature in the range of from 100 to 185 °C, and a pressure in the range of from 3- 50 mbara.
  • this distillation column (20) has from 20 to 50 theoretical stages.
  • the purified stream (J) of pipe (8) is recovered and contains L-lactide and meso-lactide of high purity.
  • the recovered purified lactide-containing stream contains 95 to 99.9 wt% lactide and more preferably 98 to 99.9 wt% lactide.
  • the purified lactide containing stream (J) to be recovered has a water content in the range of from 0 to 100 ppm and more preferably from 0 to 50 ppm, based on the total mass flow rate of the purified lactide containing stream.
  • the purified lactide containing stream has a residual acidity comprised between 0.1 to 30 mEq/kg and preferably between 0.5 and 15 mEq/kg and most preferably between 0.5 and 10 mEq/kg.
  • the overall yield in lactides unexpectedly may be equal to or higher than 90% and even higher than 95%, which is a considerable advantage over the other processes in the art.
  • the present invention also relates to an apparatus for the purification of a crude lactide-containing stream comprising:
  • the apparatus comprises:
  • the apparatus comprises:
  • FIG. 1 One embodiment of the present invention is illustrated in Figure 1 .
  • a crude-lactide containing stream (A) is led via pipe 31 to a distillation column (10).
  • distillation column (10) the crude lactide containing stream (A) is subjected to a multi-step fractionation process, thereby obtaining more volatile components such as water, lactic acid, meso-lactide and less volatile components such as liquid lactide and oligomers of lactic acid.
  • the more volatile components are withdrawn from column (10) via pipe (1) and are forming top stream (B) mainly containing water, lactic acid, meso-lactide, whereas the less volatile components will move to the lower part of distillation column (10) and are withdrawn through pipe (2).
  • a lactide containing fraction comprising volatile components is then withdrawn through side draw via pipe (3) and introduced, under the liquid phase, into melt crystallizaztion unit (4).
  • melt crystallization unit (4) a purified L-lactide containing stream (E) is recovered through pipe (5), and a drain stream (F), mainly containing meso-lactide and L-lactide, is withdrawn through pipe (7).
  • the drain stream (F) flowing through pipe (7) and top stream (B) of column (10) flowing through pipe (1) are conveyed, or combined if so desired, and sent to distillation column (20), thereby obtaining a top stream (H) with the more volatile components withdrawn through pipe (11), a stream (I) with the less volatile components withdrawn through pipe (12) and the recovery through pipe (8) of a stream (G) containing purified L-lactide, D-lactide and meso-lactide free from impurities, which is an advantage for the efficiency of the polymerisation of the lactide.
  • FIG. 2 A preferred embodiment of the present invention is illustrated in Figure 2 where the lactide containing streams (B) and (F) are supplied through pipes (1) and (7) to separation unit (20) where said both lactide containing streams (B) and (F) are subjected to a distillation operation in preferably a packed column comprising from 10 to 40, preferably 15 to 30 theoretical stages and operated at temperature comprised between 120-175 °C, preferably between 145-165 °C and at a pressure of 10 to 40 mbara, thereby obtaining a top stream (H) with the more volatile components definitly withdrawn through pipe (11) and a stream (I) with the less volatile components, including all lactide species, withdrawn through pipe (12) supplied to a third distillation column (30), preferably a packed column comprising from 6 to 20 theoretical stages and operated at a temperature of from 120 to 185 °C, preferably from 145 to 175 °C and at a pressure of from 5 to 20 mbara, from which a purified lactide stream
  • a distillation column (20) preferably a packed column comprising from 6 to 20 theoretical stages and operated at a temperature of from 120 to 185°C, preferably of from 145 to 175 °C and at a pressure of 5 to 20 mbara, so as to recover a top stream (H) flowing through pipe (11) and containing the more volatile components and all lactide species, while definitely withdrawing the heavies through the bottom stream (I) in pipe (12) for further treament ; the top stream (H) of column (20) is then supplied through pipe (11) to distillation column (30), preferably a packed column comprising from 10 to 40, preferably 15 to 30 theoretical stages and operated at a temperature comprised between 120 and 175°C, preferably between 140 and 165 °C and at a pressure of 10 to 40 mbara, from which a purified lact
  • the purified L-lactide and meso-lactide recovered by the process of the invention has a water content lower than 100 ppm, preferably lower than 50 ppm, and a residual acidity comprised between 0.1 and 30 mEq/kg, preferably comprised between 0.5 and 10 mEq/kg.
  • the operating conditions of the distillation column dedicated to the definitive removal of the most volatile components, and more particularly the inlet temperature of the lactide stream may be adjusted without departing of the process of the present invention, in view of optimizing the distillation column to balance between energy supply needed and the minimization of the degradation of the products to be recovered.
  • process of the present invention may also be applied to process for preparing PLA on the basis of the D-lactide enantiomer.
  • the invention is further illustrated by means of the following non-limiting examples.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Polyesters Or Polycarbonates (AREA)

Claims (16)

  1. Procédé destiné à la récupération et à la production de méso-lactide à partir d'un flux contenant un lactide brut, qui comprend les étapes suivantes :
    a. Exposition d'un flux de lactide brut de départ (A) à une première étape de distillation pour obtenir :
    - un flux supérieur (B) contenant principalement du méso-lactide,
    - un flux inférieur (C) et
    - un flux latéral (D) contenant principalement du L-lactide et du méso-lactide ;
    b. Récupération du flux latéral (D) et exposition dudit flux à une étape de cristallisation de la masse fondue pour obtenir :
    - un premier flux purifié (E) contenant principalement du L-lactide et
    - un flux de drainage (F) contenant principalement du méso-lactide et du L-lactide ;
    c. Récupération du flux supérieur (B) et du flux de drainage (F) ;
    d. Exposition du flux supérieur (B) et du flux de drainage (F) à une deuxième étape de distillation pour obtenir un deuxième flux purifié (G) contenant du L-lactide et du méso-lactide.
  2. Procédé selon la revendication 1, dans lequel la première étape de distillation (a) est réalisée dans une colonne de distillation, de préférence une colonne de distillation à plusieurs étages comprenant un certain nombre d'étages théoriques dans la plage située entre 6 et 30.
  3. Procédé selon la revendication 2 dans lequel la distillation de l'étape (a) est réalisée à une température de 80 à 180 °C et à une pression de 3 à 50 mbara.
  4. Procédé selon les revendications 1 à 3 dans lequel le flux latéral (D) récupéré à partir de la distillation de l'étape (a) est soumis à une étape de cristallisation de la masse fondue ayant lieu dans la plage de la température de gel du lactide et sous la température du point d'ébullition du lactide.
  5. Procédé selon les revendications 1 à 4 dans lequel les flux (B) et (F) sont transportés puis soumis à une deuxième étape de distillation pour obtenir un deuxième flux purifié (G) contenant du L-lactide et du méso-lactide, dont la teneur en énantiomère D est comprise entre 10 et 50 %.
  6. Procédé selon la revendication 5 dans lequel la deuxième étape de distillation est réalisée dans une ou plus d'une colonne de distillation, de préférence des colonnes de distillation à plusieurs étages.
  7. Procédé selon la revendication 5 dans lequel la deuxième étape de distillation est réalisée de sorte que deux flux soient récupérés : un flux supérieur contenant l'acide lactique et l'eau résiduels (H) et un flux inférieur (I), contenant le reste, y compris toutes les espèces de lactide, qui est envoyé vers une troisième étape de distillation où un flux supérieur est récupéré et comprend un mélange de L-lactide et de méso-lactide purifiés (J), dont la teneur en énantiomère D se situe dans la plage entre 10 et 50 %.
  8. Procédé selon la revendication 7 dans lequel le flux (J) de la troisième étape de distillation comprenant un mélange de L-lactide et de méso-lactide purifiés est soutiré sous la forme d'un soutirage latéral de la colonne de distillation au niveau d'un point situé entre le haut de la colonne de distillation et le haut du garnissage de ladite colonne de distillation.
  9. Procédé selon la revendication 5 dans lequel la deuxième étape de distillation est réalisée de sorte que deux flux soient récupérés, un flux inférieur contenant les composants lourds, qui est soutiré, et un flux supérieur (H) contenant l'acide lactique, l'eau et toutes les espèces de lactide résiduels, qui est alors envoyé vers une troisième étape de distillation où un flux supérieur (K) est récupéré comprenant de l'acide lactique et de l'eau, et un flux inférieur (L) comprenant un mélange d'un L-lactide et d'un méso-lactide purifiés, dont la teneur en énantiomère D se situe dans la plage entre 10 et 50 %.
  10. Procédé selon les revendications 5 à 9 dans lequel la colonne de distillation dédiée à l'élimination définitive des composants les plus volatils, tels que l'acide lactique et l'eau, comprend un certain nombre d'étages théoriques dans la plage située entre 10 et 40 et est utilisée à une température de 120 à 175 °C et à une pression de 10 à 40 mbara.
  11. Procédé selon les revendications 5 à 9 dans lequel la colonne de distillation dédiée à l'élimination définitive des composants lourds comprend un certain nombre d'étages théoriques compris entre 6 et 20 et est utilisée à une température comprise entre 120 et 185 °C et à une pression située entre 5 et 20 mbara.
  12. Procédé selon l'une quelconque des revendications 1 à 11 dans lequel un flux de lactide brut (A) est soumis à une étape de distillation dans une colonne garnie comportant de 6 à 30 étages théoriques et utilisée à 80-180 °C et à 3 à 50 mbara, à partir de laquelle sont récupérés un flux supérieur (B), un flux latéral (D) qui est en outre soumis à une cristallisation de la masse fondue pour récupérer principalement du L-lactide, et un flux inférieur (C) qui est soutiré en vue d'un traitement ultérieur, ledit flux supérieur (B) contenant principalement du méso-lactide et le flux de drainage (F) provenant de la cristallisation de la masse fondue sont alors envoyés vers une deuxième étape de distillation comprenant une première colonne de distillation garnie comportant de 10 à 40 étages théoriques et utilisée à 120 à 175 °C et à 10 à 40 mbara, pour récupérer un flux supérieur (H) comprenant de l'acide lactique et de l'eau, tandis que le flux inférieur (I) est envoyé vers une deuxième colonne de distillation garnie comprenant de 6 à 20 étages théoriques et étant utilisée à 120 à 185 °C et à 5 à 20 mbara de manière à récupérer un flux (J) de méso-lactide et de L-lactide purifiés en haut de ladite deuxième colonne tandis que le flux inférieur, contenant les composants lourds et l'oligomère de lactide, est soutiré.
  13. L-lactide et méso-lactide purifiés récupérés par le procédé tel que revendiqué dans l'une quelconque des revendications 1 à 11 dans lesquels la teneur en eau est inférieure à 100 ppm, de préférence inférieure à 50 ppm, et l'acidité résiduelle est comprise entre 0,1 et 30 mÉq/kg, de préférence comprise entre 0,5 et 10 mÉq/kg.
  14. Appareil destiné à la purification d'un flux contenant des lactides bruts comprenant :
    - Une première unité de séparation (10) qui comprend une ou plusieurs entrées, une ou plusieurs sorties, et un ou plusieurs soutirages latéraux servant à soutirer une ou plusieurs fractions contenant des lactides de l'unité de séparation ;
    - Une unité de cristallisation de la masse fondue (4) comprenant une ou plusieurs entrées et une ou plusieurs sorties ;
    - Une deuxième unité de séparation (20) comprenant une ou plusieurs entrées servant à recueillir le flux supérieur (B) provenant de l'unité de séparation (10) et le flux de drainage (F) provenant de la cristallisation de la masse fondue (4), et une ou plusieurs sorties ;
    - Facultativement, une troisième unité de séparation (30) comprenant une ou plusieurs entrées servant à recueillir la fraction lactide provenant de l'unité de séparation (20) et une ou plusieurs sorties servant à récupérer un flux de lactides purifiés.
  15. Appareil selon la revendication 14 qui comprend
    - Une première unité de séparation (10) qui comprend une ou plusieurs entrées, une ou plusieurs sorties, et un ou plusieurs soutirages latéraux servant à soutirer une ou plusieurs fractions contenant des lactides de l'unité de séparation ;
    - Une unité de cristallisation de la masse fondue (4) comprenant une ou plusieurs entrées et une ou plusieurs sorties ;
    - Une deuxième unité de séparation (20) comprenant une ou plusieurs entrées servant à recueillir le flux supérieur (B) provenant de l'unité de séparation (10) et le flux de drainage (F) provenant de la cristallisation de la masse fondue (4), et une ou plusieurs sorties servant à séparer les composants légers incluant les lactides d'une part et les composants lourds d'autre part ;
    - Une troisième unité de séparation (30) comprenant une ou plusieurs entrées servant à recueillir la fraction supérieure provenant de l'unité de séparation (20) comportant les composants légers et les lactides et une ou plusieurs sorties servant à récupérer un flux de lactides purifiés (L).
  16. Appareil selon la revendication 14 qui comprend
    - Une première unité de séparation (10) qui comprend une ou plusieurs entrées, une ou plusieurs sorties, et un ou plusieurs soutirages latéraux servant à soutirer une ou plusieurs fractions contenant des lactides de l'unité de séparation ;
    - Une unité de cristallisation de la masse fondue (4) comprenant une ou plusieurs entrées et une ou plusieurs sorties ;
    - Une deuxième unité de séparation (20) comprenant une ou plusieurs entrées servant à recueillir le flux supérieur (B) provenant de l'unité de séparation (10) et le flux de drainage (F) provenant de la cristallisation de la masse fondue (4), et une ou plusieurs sorties servant à soutirer les composants légers d'une part et les composants lourds incluant les lactides d'autre part ;
    - Une troisième unité de séparation (30) comprenant une ou plusieurs entrées servant à recueillir la fraction inférieure provenant de l'unité de séparation (20) comportant des composants lourds et les lactides et une ou plusieurs sorties servant à récupérer un flux de lactides purifiés.
EP14721873.9A 2013-05-06 2014-05-06 Procede pour recuperer et ameliorer la production du meso-lactide a partir d'un flux contenant du lactide brut Active EP2994462B2 (fr)

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EP14721873.9A EP2994462B2 (fr) 2013-05-06 2014-05-06 Procede pour recuperer et ameliorer la production du meso-lactide a partir d'un flux contenant du lactide brut

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Application Number Priority Date Filing Date Title
EP13166707 2013-05-06
PCT/EP2014/059220 WO2014180836A1 (fr) 2013-05-06 2014-05-06 Procédé de récupération et d'amélioration de la production de méso-lactide à partir d'un flux contenant du lactide brut
EP14721873.9A EP2994462B2 (fr) 2013-05-06 2014-05-06 Procede pour recuperer et ameliorer la production du meso-lactide a partir d'un flux contenant du lactide brut

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EP2994462A1 EP2994462A1 (fr) 2016-03-16
EP2994462B1 true EP2994462B1 (fr) 2016-10-19
EP2994462B2 EP2994462B2 (fr) 2019-08-21

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US (1) US9573925B2 (fr)
EP (1) EP2994462B2 (fr)
KR (1) KR102225428B1 (fr)
CN (1) CN105228994B (fr)
BR (1) BR112015027931B1 (fr)
WO (1) WO2014180836A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3406605B1 (fr) * 2017-05-22 2022-04-20 NatureWorks LLC Procedes de production de lactide avec recristallisation et recyclage de meso-lactide
CN112500389B (zh) * 2020-11-28 2022-09-20 万华化学(四川)有限公司 一种丙交酯的分离提纯方法
BE1029670B1 (fr) 2021-08-02 2023-03-06 Futerro Sa Procédé de récupération de lactide et d'acide lactique lors des étapes de production de polylactide (PLA)
EP4140978A1 (fr) 2021-08-26 2023-03-01 Futerro S.A. Procédé de préparation d'acide acrylique ou d'ester d'acide acrylique par déshydratation catalytique à partir d'un flux de recyclage d'un procédé de production d'acide polylactique
WO2023025817A1 (fr) 2021-08-26 2023-03-02 Futerro S.A. Valorisation d'un flux d'acide lactique dans le processus de production d'acide polylactique
WO2023025818A1 (fr) 2021-08-26 2023-03-02 Futerro S.A. Valorisation d'un flux d'acide d-lactique par séparation l/d dans le procédé de production d'acide l-polylactique
EP4141043A1 (fr) 2021-08-26 2023-03-01 Futerro S.A. Valorisation de flux d'acide d-lactique dans le procédé de production d'acide l-polylactique
EP4141042A1 (fr) 2021-08-26 2023-03-01 Futerro S.A. Valorisation de flux d'acide l-lactique dans la production d'acide d-polylactique

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BR112015027931A2 (pt) 2017-07-25
KR102225428B1 (ko) 2021-03-09
US9573925B2 (en) 2017-02-21
CN105228994A (zh) 2016-01-06
EP2994462A1 (fr) 2016-03-16
US20160068505A1 (en) 2016-03-10
EP2994462B2 (fr) 2019-08-21
BR112015027931A8 (pt) 2018-01-02
CN105228994B (zh) 2018-03-09
KR20160005344A (ko) 2016-01-14
BR112015027931B1 (pt) 2020-05-12
WO2014180836A1 (fr) 2014-11-13

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